U.S. patent number 8,367,792 [Application Number 13/455,442] was granted by the patent office on 2013-02-05 for polysiloxane compound and method of producing the same.
This patent grant is currently assigned to JNC Corporation. The grantee listed for this patent is Nobumasa Ootake, Kenichi Watanabe, Yasuhito Yamaryo, Kazuhiro Yoshida. Invention is credited to Nobumasa Ootake, Kenichi Watanabe, Yasuhito Yamaryo, Kazuhiro Yoshida.
United States Patent |
8,367,792 |
Ootake , et al. |
February 5, 2013 |
Polysiloxane compound and method of producing the same
Abstract
A polysiloxane represented by the formula (1) or (2):
##STR00001## where R, R.sup.1, R.sup.2, m and n are defined in the
specification.
Inventors: |
Ootake; Nobumasa (Chiba,
JP), Yoshida; Kazuhiro (Chiba, JP),
Watanabe; Kenichi (Tokyo, JP), Yamaryo; Yasuhito
(Chiba, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Ootake; Nobumasa
Yoshida; Kazuhiro
Watanabe; Kenichi
Yamaryo; Yasuhito |
Chiba
Chiba
Tokyo
Chiba |
N/A
N/A
N/A
N/A |
JP
JP
JP
JP |
|
|
Assignee: |
JNC Corporation (Tokyo,
JP)
|
Family
ID: |
39618282 |
Appl.
No.: |
13/455,442 |
Filed: |
April 25, 2012 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20120208973 A1 |
Aug 16, 2012 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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13073134 |
Mar 28, 2011 |
8173758 |
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12000615 |
Dec 14, 2007 |
7939617 |
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Foreign Application Priority Data
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Dec 15, 2006 [JP] |
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2006-339095 |
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Current U.S.
Class: |
528/34 |
Current CPC
Class: |
C08G
77/04 (20130101); C08G 77/14 (20130101) |
Current International
Class: |
C08G
77/16 (20060101) |
Field of
Search: |
;528/34 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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2006-22207 |
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Jan 2006 |
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JP |
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03/024870 |
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Mar 2003 |
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WO |
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2004/081085 |
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Sep 2004 |
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WO |
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2005/000857 |
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Jan 2005 |
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WO |
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Other References
Joseph D. Lichtenhan, "Polyhedral Oligomeric Silsesquioxanes:
Building Blocks for Silsesquioxane-Based Polymers and Hybrid
Materials", Comments Inorg. Chem., vol. 17, No. 2, pp. 115-130,
1995. cited by applicant .
Joseph D. Lichtenhan et al., "Silsesquioxane-Siloxane Copolymers
from Polyhedral Silsesquioxanes", Macromolecules, vol. 26, pp.
2141-2142, 1993. cited by applicant .
Stanley E. Anderson et al., "Structural Characterization of POSS
Siloxane Dimer and Trimer", Chem. Mater., vol. 18, pp. 1490-1497,
2006. cited by applicant.
|
Primary Examiner: Peng; Kuo-Liang
Attorney, Agent or Firm: Wenderoth, Lind & Ponack,
L.L.P.
Parent Case Text
This application is a divisional application of U.S. application
Ser. No. 13/073,134, filed Mar. 28, 2011, now U.S. Pat. No.
8,173,758, which is a divisional application of U.S. application
Ser. No. 12/000,615, filed Dec. 14, 2007, now U.S. Pat. No.
7,939,617.
Claims
The invention claimed is:
1. A polysiloxane represented by the formula (2): ##STR00042##
where in the formula (2): R independently represents alkyl having 1
to 45 carbon atoms whereby optional hydrogen may be replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, or cycloalkylene; cycloalkyl having 4 to 8 carbon
atoms; substituted or unsubstituted aryl whereby optional hydrogen
on aryl may be replaced by halogen or alkyl having 1 to 10 carbon
atoms in which optional hydrogen may be replaced by fluorine and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH--, or
phenylene; or substituted or unsubstituted arylalkyl whereby
optional hydrogen on aryl may be replaced by halogen or alkyl
having 1 to 10 carbon atoms in which optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH--, or phenylene, and alkylene of the arylalkyl
has 1 to 10 carbon atoms whereby optional hydrogen may be replaced
by fluorine and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, or phenylene; n represents an integer of 1 to 1,000;
R.sup.2 independently represents hydrogen; alkyl having 1 to 10
carbon atoms whereby optional hydrogen may be replaced by hydroxyl,
halogen, carboxyl, ester, 2,4-dioxo-3-oxacyclopentyl, acetoxy,
amino group, isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl,
cyano, vinyl, (meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or
mercapto, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH-- or phenylene; or phenyl.
2. A polysiloxane represented by the formula (2-0): ##STR00043##
where in the formula (2-0), n represents an integer of 1 to 1,000,
and R.sup.2 independently represents hydrogen; alkyl having 1 to 10
carbon atoms whereby optional hydrogen may be replaced by hydroxyl,
halogen, carboxyl, ester, 2,4-dioxo-3-oxacyclopentyl, acetoxy,
amino group, isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl,
cyano, vinyl, (meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or
mercapto, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH-- or phenylene; or phenyl.
3. A polysiloxane represented by the formula (2-1): ##STR00044##
where in the formula (2-1), n represents an integer of 1 to
1,000.
4. A method of producing a polysiloxane represented by the formula
(2-a), comprising reacting a compound represented by the formula
(1-0-1) with a compound represented by the formula (1-0-2):
##STR00045## where in the formula (1-0-1), R independently
represents alkyl having 1 to 45 carbon atoms whereby optional
hydrogen may be replaced by fluorine, and optional --CH.sub.2-- may
be replaced by --O-- or --CH.dbd.CH--; cycloalkyl having 4 to 8
carbon atoms; substituted or unsubstituted aryl whereby optional
hydrogen on aryl may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH--; or substituted or unsubstituted arylalkyl whereby
optional hydrogen on aryl may be replaced by halogen or alkyl
having 1 to 10 carbon atoms in which optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O-- or --CH.dbd.CH--, and alkylene of the arylalkyl has 1 to 10
carbon atoms, and optional --CH.sub.2-- in the alkylene may be
replaced by --O--; and in the formula (1-0-2), X represents a group
capable of reacting with silanol; ##STR00046## where in the formula
(2-a), R represents a group defined in the same manner as R in the
formula (1-0-1); and n represent an integer of 1 to 1,000.
5. A method of producing a polysiloxane represented by the formula
(2-a), comprising reacting a compound represented by the formula
(1-0-1') with a compound represented by the formula (1-0-2'):
##STR00047## where in the formula (1-0-1') and (1-0-2') M is alkali
metal, and R independently represents alkyl having 1 to 45 carbon
atoms whereby optional hydrogen may be replaced by fluorine, and
optional --CH.sub.2-- may be replaced by --O-- or --CH.dbd.CH--;
cycloalkyl having 4 to 8 carbon atoms; substituted or unsubstituted
aryl whereby optional hydrogen on aryl may be replaced by halogen
or alkyl having 1 to 10 carbon atoms in which optional hydrogen may
be replaced by fluorine, and optional --CH.sub.2-- may be replaced
by --O-- or --CH.dbd.CH--; or substituted or unsubstituted
arylalkyl whereby optional hydrogen on aryl may be replaced by
halogen or alkyl having 1 to 10 carbon atoms in which optional
hydrogen may be replaced by fluorine, and optional --CH.sub.2-- may
be replaced by --O-- or --CH.dbd.CH--, and alkylene of the
arylalkyl has 1 to 10 carbon atoms, and optional --CH.sub.2-- in
the alkylene may be replaced by --O--; and X.sup.1 represents
halogen; ##STR00048## where in the formula (2-a) R represents a
group defined in the same manner as R in the formula (1-0-1'); and
n represent an integer of 1 to 1,000.
Description
TECHNICAL FIELD
The present invention relates to a polysiloxane obtained by using a
silsesquioxane derivative and a method of producing the
polysiloxane. The polysiloxane is expected to be applied in various
fields including electronic material, optical material,
optoelectronic material, paint, and primer.
Here, the term "silsesquioxane" is a generic name for compounds in
which each silicon atom is bound to three oxygen atoms, and each
oxygen atom is bound to another silicon atom. The term
"silsesquioxane skeleton" to be used in the present invention is a
generic name for a silsesquioxane structure and a
silsesquioxane-like structure obtained by deforming part of the
silsesquioxane structure.
BACKGROUND ART
Studies have been conducted on the application of a polymer
containing a silsesquioxane skeleton to various fields because the
polymer has a specific skeleton structure. A polymer having a
silsesquioxane skeleton structure has been heretofore synthesized
by a sol-gel method involving the use of alkoxysilane such as
triethoxysilane. However, the sol-gel method involves a large
number of problems, for example, the method requires a long
reaction time, makes it difficult to control a reaction, and is apt
to leave fine holes.
Further, in recent years, a polymer using silsesquioxane having a
cage-type structure or a derivative thereof has been studied, and
the polymer is expected to have excellent weatherability, heat
resistance, physical properties, and optical properties. For
example, Lichtenhan et al. have disclosed a method of producing a
copolymer obtained by polymerizing a silsesquioxane having a
cage-type structure containing a defect, that is, a so-called
incomplete cage-type structure (a structure which is not of a
complete octahedral shape and part of which is lost) with siloxane
(U.S. Pat. Nos. 5,412,053 and 5,589,562). The production method
involves crosslinking the polyhedral oligomeric silsesquioxane by
using a bifunctional silane, siloxane, or organometallic compound
having amine etc. as a functional group. Lichtenhan et al. have
also disclosed a method of producing a copolymer having, as its
main chain, silsesquioxane of an incomplete cage-type structure
bound with siloxane etc. and a method of producing a copolymer
using silsesquioxane of a cage-type structure as a pendant
copolymer component and methacrylic acid as a copolymer main chain
component (Comments Inorg. Chem., 1995, 17 115-130). Further,
Lichtenhan et al. also disclose a method of producing a
silsesquioxane-siloxane copolymer by reacting --OH which is bound
to Si at a corner of the incomplete cage-type silsesquioxane with,
for example, bis(dimethylamino)silane (Macromolecules, 1993, 26
2141-2142). Anderson et al. have obtained a silsesquioxane oligomer
by: lithiating a silsesquioxane having silanol with n-butyllithium;
and reacting the resultant with a silsesquioxane having Si--Cl at
one site in a perfect cage-type structure (Chem. Matter., 2006,
18(6) 1490-1497).
The inventors of the present invention have reported that a
polysiloxane can be obtained from an organic silicon compound
containing silanol and referred to as a double-decker structure
alone or by reacting the compound with silane or siloxane having
Si--Cl (WO 2005/000857). Further, the inventors have reported that
a linear polymer having a perfect cage-type structure on its main
chain can be obtained by reacting a silsesquioxane having two
silanols at positions symmetric with respect to each other with a
siloxane having Si--Cl (JP 2006-22207). These documents discloses a
method of obtaining a polymer of a silsesquioxane, but these
documents describe neither a compound corresponding to a
polysiloxane containing a reactive group at a terminal of its
polymer main chain to be provided by the present specification nor
a method of producing the compound.
DISCLOSURE OF THE INVENTION
Further improvements in heat resistance, electrical insulating
property, durability, and moldability etc. have been particularly
demanded in electrical and electronic materials. However,
conventional silsesquioxane copolymers are not sufficient to
satisfy the demands for these characteristics. In view of the
foregoing, a compound having a cage-type silsesquioxane structure
as its main chain and having clearly determined binding position,
which is excellent in heat resistance, electrical insulating
property, weatherability, hardness, mechanical strength, and
chemical resistance, etc., has been demanded.
The inventors of the present invention have found that a
polysiloxane represented by the following formula (1) or (2) can be
synthesized by reacting a silsesquioxane represented by the formula
(1-0-1) with silane represented by the formula (1-0-2) at an
appropriate ratio. Further, the inventors have found that a
polysiloxane containing a reactive group at a terminal of its main
chain can be obtained by performing the reaction with, for example,
a reactive chlorosilane. Thus, the inventors have completed the
present invention.
That is, the above-mentioned problems are solved by the present
invention composed of the following constitution.
[1] A polysiloxane represented by the formula (1) or (2):
##STR00002##
In the formula (1) and (2):
R independently represents
alkyl having 1 to 45 carbon atoms whereby optional hydrogen may be
replaced by fluorine and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH--, or cycloalkylene;
cycloalkyl having 4 to 8 carbon atoms;
substituted or unsubstituted aryl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by fluorine
and optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH--,
or phenylene; or
substituted or unsubstituted arylalkyl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, or phenylene, and alkylene of the arylalkyl has 1 to
10 carbon atoms whereby optional hydrogen may be replaced by
fluorine and optional --CH.sub.2-- may be replaced by --O--,
--CH.dbd.CH--, or phenylene;
m and n independently represent an integer of 1 to 1,000;
wherein when m=1, R.sup.1 is independently selected from the group
consisting of hydroxyl, alkoxy, acetoxy, and --OSi(A).sub.3, and
when 2.ltoreq.m.ltoreq.1,000, R.sup.1 is independently selected
from the group consisting of hydrogen, hydroxyl, halogen, alkoxy,
acetoxy, --OSi(A).sub.3, and a group defined in the same manner as
R; in --OSi(A).sub.3, A independently represents hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxacyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl; and
R.sup.2 independently represents hydrogen or --Si(A).sub.3 whereby
A represents a group defined in the same manner as A in
R.sup.1.
[2] A polysiloxane represented by the formula (1-0) or (2-0):
##STR00003##
In the formula (1-0) and (2-0):
when m=1, R.sup.1 is independently selected from the group
consisting of hydroxyl, alkoxy, acetoxy, and --OSi(A).sub.3, and
when 2.ltoreq.m.ltoreq.1,000, R.sup.1 is independently selected
from the group consisting of hydrogen, hydroxyl, halogen, alkoxy,
acetoxy, --OSi(A).sub.3, alkyl having 1 to 10 carbon atoms, and
phenyl;
in --OSi(A).sub.3, A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxacyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by phenylene, --O--,
--CH.dbd.CH-- or phenylene; or
phenyl; and
R.sup.2 independently represents hydrogen or --Si(A).sub.3 whereby
A represents a group defined in the same manner as A in
R.sup.1.
[3] A polysiloxane represented by the formula (1-1):
##STR00004## In the formula (1-1), m represents an integer of 1 to
1,000.
[4] A polysiloxane represented by the formula (1-2):
##STR00005## In the formula (1-2), m represents an integer of 1 to
1,000.
[5] A polysiloxane represented by the formula (1-3):
##STR00006## In the formula (1-3), A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxacyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, an oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl; and
m represents an integer of 1 to 1,000.
[6] A polysiloxane represented by the formula (1-4):
##STR00007## In the formula (1-4), m represents an integer of 1 to
1,000.
[7] A polysiloxane represented by the formula (1-5):
##STR00008## In the formula (1-5), m represents an integer of 2 to
1,000.
[8] A polysiloxane represented by the formula (1-6):
##STR00009## In the formula (1-6), m represents an integer of 1 to
1,000.
[9] A polysiloxane represented by the formula (2-1):
##STR00010## In the formula (2-1), n represents an integer of 1 to
1,000.
[10] A polysiloxane represented by the formula (2-2):
##STR00011## In the formula (2-2),
n represents an integer of 1 to 1,000, and
A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxacyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene;
phenyl.
[11] A method of producing a polysiloxane represented by the
formula (1-a) or (2-a), comprising reacting a compound represented
by the formula (1-0-1) with a compound represented by the formula
(1-0-2):
##STR00012## In the formula (1-0-1),
R independently represents
alkyl having 1 to 45 carbon atoms whereby optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O-- or --CH.dbd.CH--;
cycloalkyl having 4 to 8 carbon atoms;
substituted or unsubstituted aryl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH--; or
substituted or unsubstituted arylalkyl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH--, and alkylene of the arylalkyl has 1 to 10 carbon
atoms, and optional --CH.sub.2-- in the alkylene may be replaced by
--O--; and
In the formula (1-0-2),
X represents a group capable of reacting with silanol;
##STR00013## In the formula (1-a) and (2-a),
R represents a group defined in the same manner as R in the formula
(1-0-1);
X represent a group defined in the same manner as X in the formula
(1-0-2); and
m and n represent an integer of 1 to 1,000.
[12] A method of producing a polysiloxane represented by the
formula (1-a') or (2-a), comprising reacting a compound represented
by the formula (1-0-1') with a compound represented by the formula
(1-0-2'):
##STR00014## In the formula (1-0-1') and (1-0-2')
M is alkali metal, and R independently represents
alkyl having 1 to 45 carbon atoms whereby optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O-- or --CH.dbd.CH--;
cycloalkyl having 4 to 8 carbon atoms;
substituted or unsubstituted aryl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH--; or
substituted or unsubstituted arylalkyl whereby optional hydrogen on
benzene ring may be replaced by halogen or alkyl having 1 to 10
carbon atoms in which optional hydrogen may be replaced by
fluorine, and optional --CH.sub.2-- may be replaced by --O-- or
--CH.dbd.CH--, and alkylene of the arylalkyl has 1 to 10 carbon
atoms, and optional --CH.sub.2-- in the alkylene may be replaced by
--O--; and
X.sup.1 represents halogen;
##STR00015## In the formula (1-a') and (2-a),
R represents a group defined in the same manner as R in the formula
(1-0-1');
X.sup.1 represents a group defined in the same manner as X.sup.1 in
the formula (1-0-2'); and
m and n represent an integer of 1 to 1,000.
[13] A method of producing a compound represented by the formula
(1-b), comprising producing a compound represented by the formula
(1-a) by the method according to [11], and hydrolyzing the
resultant compound represented by the formula (1-a):
##STR00016## In the formula (1-b),
R represents a group defined in the same manner as in the formula
(1-a); and
m represents an integer of 1 to 1,000.
[14] A method of producing a compound represented by the formula
(1-b), comprising producing a compound represented by the formula
(1-a') by the method according to [12], and hydrolyzing the
compound represented by the formula (1-a'):
##STR00017## In the formula (1-b),
R represents a group defined in the same manner as R in the formula
(1-a'); and
m represents an integer of 1 to 1,000.
[15] A method of producing a compound represented by the formula
(1-c), comprising producing a compound represented by the formula
(1-b) by the method according to [13] or [14], and reacting the
compound represented by the formula (1-b) with a compound
represented by the formula (1-0-3):
##STR00018## In the formula (1-0-3) and (1-c),
R represents a group defined in the same manner as R in the formula
(1-b);
m represents an integer of 1 to 1,000;
X represents a group capable of reacting with silanol;
A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl.
[16] A method of producing a compound represented by the formula
(1-c), comprising producing a compound represented by the formula
(1-a) by the method according to [11], and reacting the compound
represented by the formula (1-a) with a compound represented by the
formula (1-0-4):
##STR00019## In the formula (1-0-4) and (1-c),
R represents a group defined in the same manner as R in the formula
(1-a);
m represents an integer of 1 to 1,000;
A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl.
[17] A method of producing a compound represented by the formula
(1-c), comprising producing a compound represented by the formula
(1-a') by the method according to [12], and reacting the compound
represented by the formula (1-a') with a compound represented by
the formula (1-0-4):
##STR00020## In the formula (1-0-4) and (1-c),
R represents a group defined in the same manner as R in the formula
(1-a');
m represents an integer of 1 to 1,000;
A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl.
[18] A method of producing a compound represented by the formula
(2-b), comprising producing a compound represented by the formula
(2-a) by the method according to [11] or [12], and reacting the
compound represented by the formula (2-a) with a compound
represented by the formula (1-0-3):
##STR00021## In the formula (1-0-3) and (2-b),
R represents a group defined in the same manner as R in the formula
(2-a);
n represents an integer of 1 to 1,000;
X represents a group capable of reacting with silanol;
A independently represents
hydrogen;
alkyl having 1 to 10 carbon atoms whereby optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene; or
phenyl.
[19] A method of producing a compound represented by the formula
(1-d), comprising producing a compound represented by the formula
(1-c) in which at least one of A's represents hydrogen, and
remaining of A's represent alkyl having 1 to 10 carbon atoms,
phenyl, or phenylalkyl by the method according to any one of [15]
to [17], and reacting the resultant compound with a compound
represented by the formula (1-0-5):
##STR00022## In the formula (1-0-5) and (1-d),
A.sup.1 represents alkyl having 1 to 8 carbon atoms whereby
optional hydrogen may be replaced by hydroxyl, halogen, carboxyl,
ester, 2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group,
isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene;
R represents a group defined in the same manner as R in the formula
(1-c); and
at least one of A.sup.2's represents --CH.sub.2CH.sub.2A.sup.1, and
remaining of A.sup.2's are independently selected from the group
consisting of alkyl having 1 to 10 carbon atoms, phenyl, and
phenylalkyl.
[20] A method of producing a compound represented by the formula
(2-d), comprising producing a compound represented by the formula
(2-b) in which at least one of A's represents hydrogen, and
remaining of A's represent alkyl having 1 to 10 carbon atoms,
phenyl, or phenylalkyl by the method according to [18], and
reacting the resultant compound with a compound represented by the
formula (1-0-5):
##STR00023## In the formula (1-0-5) and (2-d),
A.sup.1 represents alkyl having 1 to 8 carbon atoms whereby
optional hydrogen may be replaced by hydroxyl, halogen, carboxyl,
ester, 2,4-dioxo-3-oxa-cyclopentyl, acetoxy, amino group,
isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH-- or
phenylene;
R represents a group defined in the same manner as R in the formula
(2-b); and
at least one of A.sup.2's represents --CH.sub.2CH.sub.2A.sup.1, and
remaining of A.sup.2's are independently selected from the group
consisting of alkyl having 1 to 10 carbon atoms, phenyl, and
phenylalkyl.
The terms as used herein are defined as follows. Each of alkyl and
alkylene may be linear or branched. This holds true for the case
where optional hydrogen in each of alkyl and alkylene is replaced
by halogen, cyclic group, or the like, and for the case where
optional --CH.sub.2-- in each of alkyl and alkylene is replaced by
--O--, --CH.dbd.CH--, cycloalkylene, phenylene, or the like. The
term "optional" as used herein means that not only a position but
also a number is optional. When multiple groups are replaced by
other groups, groups by which the multiple groups are replaced may
be different from each other. For example, the case when optional
--CH.sub.2-- in alkyl may be replaced by --O-- or --CH.dbd.CH--
means that the alkyl may be alkoxyalkenyl or alkenyloxyalkyl. In
addition, any one of alkoxy, alkenylene, alkenyl, and alkylene in
these groups may be linear or branched. However, in the present
invention, adjacent --CH.sub.2--, i.e., (--CH.sub.2--).sub.2 are
not replaced by (--O--).sub.2. In addition, the term "carbon
number" denotes a number of carbon atoms in the group.
Further, in the present invention, a structure in which four oxygen
is bound to Si is referred to as Q structure, a structure in which
three oxygen is bound to Si is referred to as T structure, a
structure in which two oxygen is bound to Si is referred to as D
structure, and a structure in which one oxygen is bound to Si is
referred to as M structure. Therefore, the term "T.sub.8Q.sub.2
structure" means a structure obtained by combining eight T
structures and two Q structures.
According to the present invention, a polysiloxane compound having,
on its main chain, a silsesquioxane skeleton having
Q(T.sub.8Q).sub.n structure or T.sub.8(QT.sub.8).sub.n structure
can be obtained. Further, a polysiloxane compound having, for
example, M.sub.2Q(T.sub.8Q).sub.nM.sub.2 structure,
DT.sub.8(QT.sub.8).sub.nD structure, or
M.sub.2T.sub.8(QT.sub.8).sub.nM.sub.2 structure can be obtained by
capping the resultant polysiloxane with a silicon compound
containing a reactive group. Further, an organic-inorganic
composite material can be produced by using the resultant
polysiloxane.
DESCRIPTION OF THE PREFERABLE EMBODIMENTS
In the following description, a silicon compound represented by the
formula (1) may be represented as Compound (1), and a compound
represented by the formula (2) may be represented as Compound (2).
A compound represented by any other formula may also be simply
represented in the same manner as that described above.
Hereinafter, the present invention will be described in more
detail.
A polysiloxane provided by the present invention is represented by
the formula (1) or (2).
##STR00024## In the formula (1) and (2):
R independently represents alkyl having 1 to 45 carbon atoms,
cycloalkyl having 4 to 8 carbon atoms, substituted or unsubstituted
aryl, or substituted or unsubstituted arylalkyl.
The alkyl having 1 to 45 carbon atoms has preferably 1 to 30, or
more preferably 1 to 8 carbon atoms. In addition, optional hydrogen
in the alkyl may be replaced by fluorine, and optional --CH.sub.2--
in the alkyl may be replaced by --O--, --CH.dbd.CH--, or
cycloalkylene.
Examples of the unsubstituted alkyl having 1 to 30 carbon atoms
include methyl, ethyl, propyl, 1-methylethyl, butyl,
2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl,
1,1,2-trimethylpropyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl,
decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl,
docosyl, and triacontyl.
Examples of fluorinated alkyl having 1 to 30 carbon atoms include a
3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl,
tridecafluoro-1,1,2,2-tetrahydrooctyl,
heptadecafluoro-1,1,2,2-tetrahydrodecyl,
perfluoro-1H,1H,2H,2H-dodecyl, and perfluoro-1H,1H, 2H,
2H-tetradecyl.
Examples of cycloalkyl having 4 to 8 carbon atoms include
cyclohexyl, cyclopentyl, 2-bicycloheptyl, and cyclooctyl.
In the case where R in the formula (1) is substituted or
unsubstituted aryl, optional hydrogen may be replaced by halogen or
alkyl having 1 to 10 carbon atoms. Preferable examples of halogen
include fluorine, chlorine, and bromine. In the alkyl having 1 to
10 carbon atoms, optional hydrogen may be replaced by fluorine, and
optional --CH.sub.2-- may be replaced by --O--, --CH.dbd.CH--, or
phenylene. That is, preferable examples of substituted or
unsubstituted aryl represented by R include phenyl, alkylphenyl,
alkyloxyphenyl, alkenylphenyl, phenyl having, as a substituent,
alkyl containing 1 to 10 carbon atoms in which optional
--CH.sub.2-- is replaced by phenylene. In each of the groups listed
here, optional hydrogen on benzene ring may be replaced by halogen.
Note that "phenyl" in the present invention denotes unsubstituted
phenyl if not specified.
Examples of halogenated phenyl include pentafluorophenyl,
4-chlorophenyl, and 4-bromophenyl. Examples of alkylphenyl include
4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl,
4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl,
4-decylphenyl, 2,4-dimethylphenyl, 2,4,6-trimethylphenyl,
2,4,6-triethylphenyl, 4-(1-methylethyl)phenyl,
4-(1,1-dimethylethyl)phenyl, 4-(2-ethylhexyl)phenyl, and
2,4,6-tris(1-methylethyl)phenyl. Examples of alkyloxyphenyl include
4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl,
4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyloxyphenyl,
4-octadecyloxyphenyl, 4-(1-methylethoxy)phenyl,
4-(2-methylpropoxy)phenyl, and 4-(1,1-dimethylethoxy)phenyl.
Examples of the alkenylphenyl include 4-ethenylphenyl,
4-(1-methylethenyl)phenyl, and 4-(3-butenyl)phenyl.
Examples of phenyl having, as a substituent, alkyl containing 1 to
10 carbon atoms in which optional --CH.sub.2-- is replaced by
phenylene include 4-(2-phenylethenyl)phenyl, 4-phenyloxyphenyl,
3-phenylmethylphenyl, biphenyl, and terphenyl.
4-(2-phenylethenyl)phenyl is an example of ethylphenyl in which one
--CH.sub.2-- is replaced by phenylene and another --CH.sub.2-- is
replaced by --CH.dbd.CH--.
Examples of phenyl in which some of hydrogen on benzene ring is
replaced by halogen and other hydrogen is replaced by alkyl,
alkyloxyl, or alkenyl include 3-chloro-4-methylphenyl,
2,5-dichloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl,
2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl,
3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl,
3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl,
3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl,
3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl,
2,3-difluoro-4-ethyoxyphenyl, 2,3-difluoro-4-propoxyphenyl, and
4-ethenyl-2,3,5,6-tetrafluorophenyl.
When any one of R in the formula (1) represents substituted or
unsubstituted arylalkyl, alkylene of the arylalkyl has 1 to 10
carbon atoms, optional hydrogen in the alkylene may be replaced by
fluorine, and optional --CH.sub.2-- in the alkylene may be replaced
by --O--, --CH.dbd.CH--, or cycloalkylene. A preferable example of
the arylalkyl is phenylalkyl.
Specific examples of unsubstituted phenylalkyl include
phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl,
5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl, 1-phenylethyl,
2-phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl,
3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl,
2-methyl-2-phenylpropyl, and 1-phenylhexyl.
In the phenylalkyl, optional hydrogen on benzene ring may be
replaced by halogen or alkyl having 1 to 10 carbon atoms. In the
alkyl having 1 to 10 carbon atoms, optional hydrogen may be
replaced by fluorine, and optional --CH.sub.2-- may be replaced by
--O--, --CH.dbd.CH--, or phenylene.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by fluorine include 4-fluorophenylmethyl,
2,3,4,5,6-pentafluorophenylmethyl,
2-(2,3,4,5,6-pentafluorophenyl)ethyl,
3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorophenyl)propyl,
and a 2-(4-fluorophenyl)propyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by chlorine include 4-chlorophenylmethyl,
2-chlorophenylmethyl, 2,6-dichlorophenylmethyl,
2,4-dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl, a
2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, a
2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl,
2-(2-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl,
2-(2,4,5-chlorophenyl)ethyl, 2-(2,3,6-chlorophenyl)ethyl,
3-(3-chlorophenyl)propyl, 3-(4-chlorophenyl)propyl,
3-(2,4,5-trichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)propyl, a
4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl,
4-(4-chlorophenyl)butyl, 4-(2,3,6-trichlorophenyl)butyl,
4-(2,4,5-trichlorophenyl)butyl, a 1-(3-chlorophenyl)ethyl,
1-(4-chlorophenyl)ethyl, 2-(4-chlorophenyl)propyl,
2-(2-chlorophenyl)propyl, and 1-(4-chlorophenyl)butyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by bromine include 2-bromophenylmethyl,
4-bromophenylmethyl, 2,4-dibromophenylmethyl,
2,4,6-tribromophenylmethyl, 2,3,4,5-tetrabromophenylmethyl,
2,3,4,5,6-pentabromophenylmethyl, 2-(4-bromophenyl)ethyl,
3-(4-bromophenyl)propyl, 3-(3-bromophenyl)propyl,
4-(4-bromophenyl)butyl, 1-(4-bromophenyl)ethyl,
2-(2-bromophenyl)propyl, and 2-(4-bromophenyl)propyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms
include 2-methylphenylmethyl, 3-methylphenylmethyl,
4-methylphenylmethyl, 4-dodecylphenylmethyl,
(3,5-dimethylphenylmethyl, 2-(4-methylphenyl)ethyl,
2-(3-methylphenyl)ethyl, 2-(2,5-dimethylphenyl)ethyl,
2-(4-ethylphenyl)ethyl, 2-(3-ethylphenyl)ethyl,
1-(4-methylphenyl)ethyl, 1-(3-methylphenyl)ethyl,
1-(2-methylphenyl)ethyl, 2-(4-methylphenyl)propyl,
2-(2-methylphenyl)propyl, 2-(4-ethylphenyl)propyl,
2-(2-ethylphenyl)propyl, 2-(2,3-dimethylphenyl)propyl,
2-(2,5-dimethylphenyl)propyl, 2-(3,5-dimethylphenyl)propyl,
2-(2,4-dimethylphenyl)propyl, 2-(3,4-dimethylphenyl)propyl,
2-(2,5-dimethylphenyl)butyl, 4-(1-methylethyl)phenylmethyl,
2-(4-(1,1-dimethylethyl)phenyl)ethyl,
2-(4-(1-methylethyl)phenyl)propyl, and
2-(3-(1-methylethyl)phenyl)propyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms and
hydrogen in the alkyl is replaced by fluorine include
3-trifluoromethylphenylmethyl, 2-(4-trifluoromethylphenyl)ethyl,
2-(4-nonafluorobutylphenyl)ethyl,
2-(4-tridecafluorohexylphenyl)ethyl,
2-(4-heptadecafluorooctylphenyl)ethyl,
1-(3-trifluoromethylphenyl)ethyl, 1-(4-trifluoromethylphenyl)ethyl,
1-(4-nonafluorobutylphenyl)ethyl,
1-(4-tridecafluorohexylphenyl)ethyl,
1-(4-heptadecafluorooctylphenyl)ethyl,
2-(4-nonafluorobutylphenyl)propyl,
1-methyl-1-(4-nonafluorobutylphenyl)ethyl,
2-(4-tridecafluorohexylphenyl)propyl,
1-methyl-1-(4-tridecafluorohexylphenyl)ethyl,
2-(4-heptadecafluorooctylphenyl)propyl, and
1-methyl-1-(4-heptadecafluorooctylphenyl)ethyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms and
--CH.sub.2-- in the alkyl is replaced by --CH.dbd.CH-- include
2-(4-ethenylphenyl)ethyl, 1-(4-ethenylphenyl)ethyl, and
1-(2-(2-propenyl)phenyl)ethyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms and
--CH.sub.2-- in the alkyl is replaced by --O-- include
4-methoxyphenylmethyl, 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl,
2-(4-methoxyphenyl)ethyl, 3-(4-methoxyphenyl)propyl,
3-(2-methoxyphenyl)propyl, 3-(3,4-dimethoxyphenyl)propyl,
11-(4-methoxyphenyl)undecyl, 1-(4-methoxyphenyl)ethyl,
(3-methoxymethylphenyl)ethyl, and
3-(2-nonadecafluorodecenyloxyphenyl)propyl.
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms and
one --CH.sub.2-- in the alkyl is replaced by cycloalkylene include
cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl,
cyclohexylphenylmethyl, cyclohexylphenylethyl,
cyclohexylphenylpropyl, and cyclohexyloxyphenylmethyl (the case
where another --CH.sub.2-- of the alkyl is replaced by --O-- is
also included in these examples).
Specific examples of phenylalkyl in which optional hydrogen on
benzene ring is replaced by alkyl having 1 to 10 carbon atoms and
one --CH.sub.2-- in the alkyl is replaced by phenylene include
2-(4-phenoxyphenyl)ethyl, 2-(4-phenoxyphenyl)propyl,
2-(2-phenoxyphenyl)propyl, 4-biphenylylmethyl, 3-biphenylylethyl,
4-biphenylylethyl, 4-biphenylylpropyl, 2-(2-biphenylyl)propyl, and
2-(4-biphenylyl)propyl (the case where another --CH.sub.2-- of the
alkyl is replaced by --O-- is also included in these examples).
Specific examples of phenylalkyl in which at least two hydrogen of
benzene ring is replaced by different groups include
3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl,
3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl,
5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl,
2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl,
2,3-dichloro-4-methylphenylmethyl,
2,5-dichloro-4-methylphenylmethyl,
3,5-dichloro-4-methylphenylmethyl,
2,3,5-trichloro-4-methylphenylmethyl,
2,3,5,6-tetrachloro-4-methylphenylmethyl,
2,3,4,6-tetrachloro-5-methylphenylmethyl,
2,3,4,5-tetrachloro-6-methylphenylmethyl,
4-chloro-3,5-dimethylphenylmethyl,
2-chloro-3,5-dimethylphenylmethyl,
2,4-dichloro-3,5-dimethylphenylmethyl,
2,6-dichloro-3,5-dimethylphenylmethyl,
2,4,6-trichloro-3,5-dimethylphenylmethyl,
3-bromo-2-methylphenylmethyl, 4-bromo-2-methylphenylmethyl,
5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl,
3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl,
2,3,5-tribromo-4-methylphenylmethyl,
2,3,5,6-tetrabromo-4-methylphenylmethyl, and
11-(3-chloro-4-methoxyphenyl)undecyl.
In addition, particularly preferable examples of phenyl in
phenylalkyl include: unsubstituted phenyl; and phenyl having as a
substituent at least one of fluorine, alkyl having 1 to 4 carbon
atoms, ethenyl, and methoxy. Specific examples of phenylalkyl in
which --CH.sub.2-- of alkylene is replaced by --O--, --CH.dbd.CH--,
or cycloalkylene include 3-phenoxypropyl, 1-phenylethenyl,
2-phenylethenyl, 3-phenyl-2-propenyl, 4-phenyl-4-pentenyl,
13-phenyl-12-tridecenyl, phenylcyclohexyl, and phenoxycyclohexyl.
Examples of phenylalkenyl in which hydrogen on benzene ring is
replaced by fluorine or methyl include 4-fluorophenylethenyl,
2,3-difluorophenylethenyl, 2,3,4,5,6-pentafluorophenylethenyl, and
4-methylphenylethenyl.
Of these groups, preferable R is selected from the group consisting
of alkyl having 1 to 45 carbon atoms, substituted or unsubstituted
phenyl, and substituted or unsubstituted phenylalkyl. Amore
preferable example of R is selected from the group consisting of
substituted or unsubstituted phenyl and substituted or
unsubstituted phenylalkyl.
Alkylene of the substituted or unsubstituted phenylalkyl has
preferably 1 to 8 carbon atoms, optional hydrogen on benzene ring
in the phenylalkyl may be replaced by fluorine or alkyl having 1 to
4 carbon atoms, and optional --CH.sub.2-- in the alkylene may be
replaced by --O--, --CH.dbd.CH--, or cycloalkylene.
When phenyl in each of these groups has multiple substituents, the
substituents may be identical to or different from each other. In
addition, all of R's in the formula (1) is preferably the same
group selected from these preferable examples.
Still more preferable examples of R include phenyl, halogenated
phenyl, phenyl having at least one methyl, methoxyphenyl,
phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl,
1-methyl-2-phenylethyl, pentafluorophenylpropyl,
4-ethylphenylethyl, 3-ethylphenylethyl,
4-(1,1-dimethylethyl)phenylethyl, 4-ethenylphenylethyl,
1-(4-ethenylphenyl)ethyl, and 4-methoxyphenylpropyl. Of these,
phenyl is particularly preferable.
Next, m in the formula (1) will be explained. m represents an
integer of 1 to 1,000, or preferably 1 to 100.
When m represents 1, R.sup.1 is independently selected from the
group consisting of hydroxyl, alkoxy, acetoxy, and
--OSi(A).sub.3.
When m represents 2 to 1,000, R.sup.1 is independently selected
from the group consisting of hydrogen, hydroxyl, halogen, alkoxy,
acetoxy, --OSi(A).sub.3, and a group defined in the same manner as
R.
When any one of R.sup.1's represents --OSi(A).sub.3, A
independently represents hydrogen; alkyl having 1 to 10 carbon
atoms in which optional hydrogen may be replaced by hydroxyl,
halogen, carboxyl, ester, 2,4-dioxo-3-oxacyclopentyl, acetoxy,
amino group, isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl,
cyano, vinyl, (meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or
mercapto; or phenyl. Optional --CH.sub.2-- in the alkyl may be
replaced by --O--, --CH.dbd.CH-- or phenylene. It should be noted
that hydrogen of each of hydroxyl, carboxyl, amino group, and
mercapto may be replaced by, for example, trimethylsilyl.
It should be noted that two of A's may form dicarboxylic
anhydride.
n in the formula (2) represents an integer of 1 to 1,000, and
preferably 1 to 100. R.sup.2 is independently selected from the
group consisting of hydrogen and --Si(A).sub.3.
When any one of R.sup.2's represents --OSi (A).sub.3, A
independently represents hydrogen; alkyl having 1 to 10 carbon
atoms in which optional hydrogen may be replaced by hydroxyl,
halogen, carboxyl, ester, 2,4-dioxo-3-oxacyclopentyl, acetoxy,
amino group, isocyanate, oxiranyl, 3,4-epoxycyclohexyl, oxetanyl,
cyano, vinyl, (meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or
mercapto; or phenyl. Optional --CH.sub.2-- in the alkyl may be
replaced by --O--, --CH.dbd.CH-- or phenylene. It should be noted
that hydrogen of each of hydroxyl, carboxyl, amino group, and
mercapto may be replaced by, for example, trimethylsilyl. It should
be noted that two of A's may form dicarboxylic anhydride.
To be specific, A is independently selected from the
followings.
##STR00025##
In these formula, ma represents an integer of 2 to 10, na
represents an integer of 0 to 15, q represents an integer of 2 or
3, r represents an integer of 2 to 200, t represents an integer of
1 to 3, and E represents hydrogen or alkyl having 1 to 4 carbon
atoms. In the above examples, each of --CF.sub.3 is bound to
benzene ring at an optional position. r represents an integer of
preferably 2 to 100, more preferably 2 to 20.
Particularly preferable examples of the polysiloxane represented by
the formula (1) or (2) include the following compounds; provided
that the compound of the present invention is not limited to the
following compounds.
##STR00026##
It should be noted that A in the formula (1-3) represents a group
defined in the same manner as A in --Si (A).sub.3 of the above
formula (1) and (2). In the formula (1-1), (1-2), (1-3), (1-4) and
(1-6), m represents an integer of 1 to 1,000. In the formula (1-5),
m represents an integer of 2 to 1,000.
Next, a method of producing a compound in which any one of
R.sup.1's in the formula (1) is alkoxy, acetoxy, halogen, or
hydroxyl will be described.
Such compound can be represented as a formula (1-a) or (1-b) shown
in the following reaction formula (I), and can be obtained by
reacting a compound represented by the formula (1-0-1) which is
obtainable by the method disclosed by the inventors of the present
invention (Japanese Patent Application Laid-open No. 2006-182650)
with a silane compound represented by the formula (1-0-2) which is
commercially available, in an organic solvent in such a manner that
a mixing ratio of the number of moles (N) of Compound (1-0-2) to
the number of moles (M) of Compound (1-0-1) is not less than 1, and
preferably 1 to 10.
The organic solvent that can be used in the reaction is not
particularly limited as long as the solvent does not inhibit the
progress of the reaction. Examples of a preferable organic solvent
include: ethers such as diethyl ether, tetrahydrofuran (THF), and
dioxane; and esters such as methyl acetate, ethyl acetate, and
butyl acetate. One kind thereof may be used alone, or two or more
kinds thereof may be used in combination.
The volume of the organic solvent is not particularly limited in
the present invention, but the volume is preferably such that the
solid content concentration of a reaction solution is 1% to 50% in
consideration of the efficient production of the compound.
##STR00027##
Here, X in the formula (1-0-2) independently represents a group
capable of reacting with silanol, and specifically represents
halogen, alkoxy, or acetoxy. Specific examples of the Compound
(1-0-2) include tetramethoxysilane, tetraethoxysilane,
tetraisopropoxysilane, tetrachlorosilane, tetrabromosilane,
tetraiodosilane, and tetraacetoxysilane. Of these,
tetrachlorosilane and tetraacetoxysilane are preferable because
these compounds are easily commercially available.
Then, Compound (1-a) thus obtained is hydrolyzed by using an acid
such as hydrochloric acid, acetic acid, or sulfuric acid as a
catalyst as required, thereby Compound (1-b) can be obtained.
##STR00028##
Next, a method of producing Compound (1-c) in which: any one of
R.sup.1's in the formula (1) represents --OSi (A).sub.3; whereby A
independently represents (i) hydrogen (bound to Si), (ii) alkyl
having 1 to 10 carbon atoms in which optional hydrogen may be
replaced by hydroxyl, halogen, carboxyl, ester,
2,4-dioxo-3-oxacyclopentyl, acetoxy, amino group, isocyanate,
oxiranyl, 3,4-epoxycyclohexyl, oxetanyl, cyano, vinyl,
(meth)acryloyl, 4-vinylphenyl, alkyleneoxy, or mercapto and
optional --CH.sub.2-- in the alkyl may be replaced by --O--,
--CH.dbd.CH-- or phenylene, or (iii) phenyl will be described.
Such compound can be obtained by reacting Compound (1-b) with
Compound (1-0-3) in organic solvent preferably in the presence of
tertiary amine (NR.sub.3) as shown in the formula (II).
Organic solvent to be used for the reaction is not particularly
limited as long as it does not inhibit the progress of the
reaction. Examples of preferable solvent include: aliphatic
hydrocarbons such as hexane and heptane; aromatic hydrocarbons such
as benzene, toluene, and xylene; ethers such as diethyl ether,
tetrahydrofuran (THF), and dioxane; halogenated hydrocarbons such
as methylene chloride and carbon tetrachloride; and esters such as
ethyl acetate. Of these, organic solvents such as aromatic
hydrocarbons and ethers are more preferable and toluene and THF are
still more preferable.
Further, the reaction can be easily promoted by adding tertiary
amine such as triethylamine. The addition amount of the tertiary
amine is not particularly limited as long as the reaction can be
progressed, but the addition amount of triethylamine is, for
example, 0.1 to 10 fold moles, or preferably 1 to 5 fold moles with
respect to Compound (1-0-3).
##STR00029##
Next, a method of producing Compound (1) in which: any one of
R.sup.1's in the formula (1) represents --OSi(A).sub.3 whereby at
least one of A's independently represents (i) alkyl having 2 to 10
carbon atoms in which optional hydrogen may be replaced by
hydroxyl, halogen, ester, cyano, vinyl, acetoxy, (meth)acryloyl,
carboxyl, amino group, isocyanate, oxiranyl, 3,4-epoxycyclohexyl,
oxetanyl, mercapto, 2,4-dioxo-3-oxacyclopentyl, or alkyleneoxy and
optional --CH.sub.2-- in the alkyl may be replaced by --O--,
--CH.dbd.CH-- or phenylene, or (ii) phenyl; and the remaining of
A's independently represent alkyl having 1 to 10, phenyl or
phenylalkyl carbon atoms will be described.
As shown below, such compound can be obtained through two steps. At
first, Compound (1-c) in which at least one of A's represents
hydrogen and the remaining of A's represent alkyl having 1 to 10
carbon atoms, phenyl or phenylalkyl is synthesized by reacting
Compound (1-b) with Compound (1-0-3) in which at least one of A's
represents hydrogen and the remaining of A's independently
represent alkyl having 1 to 10 carbon atoms, phenyl, or phenylalkyl
in the same manner as the above-mentioned method.
Specific examples of "Compound (1-0-3) in which at least one of A's
represents hydrogen and the remaining of A's independently
represent alkyl having 1 to 10 carbon atoms or phenyl" include
dimethylchlorosilane, diethylchlorosilane, methylethylchlorosilane,
methylhexylchlorosilane, diisopropylchlorosilane,
di-t-butylchlorosilane, dicyclopentylchlorosilane,
dicyclohexylchlorosilane, dinormaloctylchlorosilane,
methylphenylchlorosilane, and diphenylchlorosilane.
Secondly, as shown in a formula (III), Compound (1-c) obtained in
the first step is reacted with Compound (1-0-5) as shown below in
organic solvent in the presence of hydrosilylation catalyst,
thereby Compound (1-d) is obtained.
##STR00030##
In the formula (1-0-5), A.sup.1 represents alkyl having 1 to 8
carbon atoms whereby optional hydrogen may be replaced by hydroxyl;
halogen; carboxyl; ester; 2,4-dioxo-3-oxa-cyclopentyl; acetoxy;
amino group; isocyanate; oxiranyl; 3,4-epoxycyclohexyl; oxetanyl;
cyano; vinyl; (meth)acryloyl; 4-vinylphenyl; alkyleneoxy; or
mercapto; and optional --CH.sub.2-- in the alkyl may be replaced by
--O--, --CH.dbd.CH-- or phenylene. It should be noted that hydrogen
of each of hydroxyl, carboxyl, amino group, and mercapto may be
replaced by, for example, trimethylsilyl.
R in the formula (1-d) represents a group defined in the same
manner as R in the formula (1-c). At least one of A.sup.2's
represents --CH.sub.2CH.sub.2A.sup.1, and the remaining of
A.sup.2's represent are independently selected from alkyl having 1
to 10 carbon atoms, phenyl, and phenylalkyl.
Examples of the compound represented by (1-0-5) having both of
hydroxyl and alkenyl include allyl alcohol, 3-buten-1-ol,
3-buten-2-ol, ethyleneglycol monovinylether, ethyleneglycol
monoallylether, diethyleneglycol monoallylether, glycerine
monoallylether, trimethylolethane monoallylether,
trimethylolpropane monoallylether, polyethyleneglycol
monoallylether, polypropyleneglycol monoallylether,
1-ethenyl-cyclobutanol, 2-ethenyl-cyclobutanol,
3-ethenyl-cyclobutanol, vinylphenol, 2-allylphenol, 4-allylphenol,
4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol,
4-(2-propenyl)-1,2-benzenediol, and
4-(2,4-dihydroxyphenyl)-3-butene-2-one. The hydroxyl of these
compounds may be protected as cyclic or branched-chain carbonyl
having 3 to 30 carbon atoms, ester, ether, acetal, ketal, or
silylether. Of these compounds, preferable are allylalcohol,
ethyleneglycol monoallylether, glycerine monoallylether,
trimethylolpropane monoallylether, 2-allylphenol, and 4-allylphenol
because of easily availability.
Examples of the compound represented by (1-0-5) having carboxyl and
alkenyl include (meth)acrylic acid, crotonic acid, isocrotonic
acid, vinyl acetate, 3-butenoic acid, 2-methyl-3-butenoic acid,
2,2-dimethyl-3-butenoic acid, 2-n-propyl-3-pentenoic acid,
4-pentenoic acid, 3-methyl-4-pentenoic acid,
2,2-dimethyl-4-pentenoic acid, 3,3-dimethyl-4-pentenoic acid,
4-hexenoic acid, 5-hexenoic acid, 2,6-heptadienoicacid,
7-octenoicacid, 8-nonenoicacid, 9-decenoic acid, 10-undecenoic
acid, 11-dodecenoic acid, propiolic acid, 2-butynoic acid, maleic
acid, fumaric acid, acethylene carboxylic acid, 2-vinyl benzoate,
3-vinyl benzoate, 4-vinyl benzoate, and 4-allyl-2,3,5,6-tetrafluoro
benzoate. Herein, (meth)acrylic acid refers to acrylic acid and
methacrylic acid. The carboxyl group of these compounds may be
protected as ester, or trialkyl silyl. Of these compounds,
preferable are (meth)acrylic acid, vinylacetate, 4-pentenoic acid,
10-undecenoic acid, and 4-vinyl benzoate because of easily
availability.
Examples of the compound represented by (1-0-5) having both of
isocyanate and alkenyl include vinyl isocyanate, allyl isocyanate,
3-isocyanate-2-methyl-1-propene, methacryloyl isocyanate,
isocyanate ethylmethacrylate, vinylbenzyl isocyanate,
3-isocyanate-1-butene, 3-isocyanate-3-methyl-1-butene,
4-isocyanate-2-methyl-1-butene, 4-isocyanate-3,3-dimethyl-1-butene,
4-isocyanate-4-methyl-1-pentene, and 5-isocyanate-1-pentene. Of
these compounds, preferable are vinyl isocyanate, allyl isocyanate,
and methacryloyl isocynate because of easily availability.
Examples of the compounds represented by (1-0-5) having both of
oxiranyl and alkenyl include allylglycidyl ether,
2-methylallylglycidyl ether, vinylglycidyl ether, glycideyl
maleate, glycidyl itaconate, glycidyl acrylate, glycidyl
methacrylate, 1,2-epoxy-6-heptene, 1,2-epoxy-3-butene,
2-cyclohexene-1-glycidyl ether,
cyclohexene-4,5-glycidylcarboxylate, cyclohexene-4-glycidyl
carboxylate, 5-norbornene-2-methyl-2-glycidyl carboxylate, and
endocis-bicyclo[2.2.1]-5-heptene-2,3-diglycidyl dicarboxylate.
Preferable is allyl glycidyl ether because of easily
availability.
Examples of Compound (1-0-5) having mercapto and alkenyl include
allyl mercaptan and 2-methyl-2-propene-1-thiol.
Examples of Compound (1-0-5) having 2,4-dioxo-3-oxacyclopentyl and
alkenyl include allylsuccinic anhydride, isobutylsuccinic
anhydride, isobutenylsuccinic anhydride,
bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, and
5-norbornene-2,3-dicarboxylic anhydride. Of these compounds,
allylsuccinic anhydride and 5-norbornene-2,3-dicarboxylic anhydride
are preferable in consideration of easy availability.
The compound represented by compound (1-0-5) having alkyleneoxy and
alkenyl is commercially available from NOF CORPORATION and the
like. In the case of polyethylene glycol monoallyl ether, UNIOX
PKA-5001, PKA-5002, PKA-5003, PKA-5004, and PKA-5005 are
exemplified. In the case of methoxypolyethylene glycol allylether,
UNIOX PKA-5006, PKA-5007, PKA-5008, PKA-5009, and PKA-5010 are
exemplified. In the case of polypropylene glycol monoallylether,
UNISAFE PKA-5014 is exemplified. In the case of polyethylene glycol
polypropylene glycol allylether, UNISAFE PKA-5011, PKA-5012, and
PKA-5013 are exemplified. If there is no commercially available
product for some compounds, allylether having alkyleneoxy can be
obtained by reacting polyalkylene glycol or monoether compound
thereof with sodium hydride to produce sodium alcoholate, thereby
reacting it with allylbromide.
Examples of Compound (1-0-5) having amino group and alkenyl include
allylamine, butenylamine, hexenylamine, octenylamine, and
decenylamine.
Examples of compound (1-0-5) containing oxcetanyl and alkenyl
include 3-vinyl oxcetane, 3-methyl-3-vinyl oxcetane,
3-ethyl-3-vinyl oxcetane, 3-allyloxcetane,
3-allyl-3-methyloxcetane, 3-allyl-3-ethyloxcetane,
[(3-oxcetanyl)methyl]vinyl ether,
[(3-methyl-3-oxcetanyl)methyl]vinyl ether,
[(3-ethyl-3-oxcetanyl)methyl]vinyl ether, 3-allyloxymethyl
oxcetane, 3-allyloxymethyl-3-methyloxcetane,
3-allyloxymethyl-3-ethyloxcetane, 3-allyloxyethyl oxcetane,
3-allyloxyethyl-3-methyloxcetane, and
3-allyloxyethyl-3-ethyloxcetane. Particularly preferable are
3-allyloxymethyl oxcetane, 3-allyloxymethyl-3-methyloxcetane,
3-alyloxymethyl-3-ethyloxcetane, 3-allyloxymethyloxcetane,
3-allyloxyethyl-3-methyloxcetane, and
3-allyloxyethyl-3-ethyloxcetane.
The above-mentioned first step of obtaining Compound (1-c) may be
performed by a method involving reacting Compound (1-a) with
Compound (1-0-4) shown below or by a method involving reacting
Compound (1-a') with Compound (1-0-4).
One of Compounds (1-0-5) having any one of the above-mentioned
functional groups and alkenyl is allowed to react with Compound
(1-c) in which at least one of A's represents hydrogen and the
remaining of A's independently represent alkyl having 1 to 10
carbon atoms or phenyl, thereby Compound (1-d) in which at least
one of A's represents --CH.sub.2CH.sub.2A', and the remaining of
A's independently represent alkyl having 1 to 10 carbon atoms or
phenyl is obtained. Reacting at least two kinds of Compounds
(1-0-5) each having any one of the functional groups with Compound
(1-c) in which at least two of A represents hydrogen suffices for
the synthesis of Compound (1-d) having at least two different
functional groups. In this case, Compound (1-d) can be obtained by
reacting two kinds of Compounds (1-0-5) having the functional group
with Compound (1-c) in mixture or by reacting the first Compound
(1-0-5) and the second Compound (1-0-5) with Compound (1-c)
sequentially in consideration of a difference in reactivity of the
two kinds of Compounds (1-0-5).
A solvent to be used in the hydrosilylation reaction between
Compound (1-c) in which at least one of A's represents hydrogen and
the remaining of A's independently represent alkyl having 1 to 10
carbon atoms or phenyl and Compound (1-0-5) having the functional
group is not particularly limited as long as the solvent does not
inhibit the reaction. Preferable examples of the solvent include:
aliphatic hydrocarbons such as hexane and heptane; aromatic
hydrocarbons such as benzene, toluene, and xylene; ethers such as
diethyl ether, tetrahydrofuran (THF), and dioxane; halogenated
hydrocarbons such as methylene chloride and carbon tetrachloride;
and esters such as methyl acetate and ethyl acetate. Each of these
solvents may be used alone, or two or more thereof may be used in
combination. Of these solvents, the aromatic hydrocarbons are
preferable, and, of the aromatic hydrocarbons, toluene is
particularly preferable.
Although the reaction between Compound (1-c) and Compound (1-0-5)
having the functional group does not necessarily require a solvent,
solvent, if used, is prepared so as to have a concentration of
preferably 0.05 to 80 wt %, or more preferably 30 to 70 wt %.
The ratio of Compound (1-0-5) having the functional group with
respect to Compound (1-c) varies depending on purposes. For
example, when each of all SiH groups of Compound (1-c) is allowed
to react with Compound (1-0-5), the number of moles of Compound
(1-0-5) must be equal to or larger than the number of moles of SiH
groups of Compound (1-c). In addition, when part of --SiH groups
are left, the number of moles of the Compound (1-0-5) having the
functional group has only to be equal to or smaller than the number
of moles of Compound (1-c).
The reaction may be performed at room temperature, or may be
performed under heating so that the reaction is promoted. In
addition, the reaction system may be cooled as required for
controlling a secondary reaction due to heat of the reaction.
Next, hydrosilylation catalyst to be used in the hydrosilylation
reaction in the present invention will be described. A compound
containing a transition metal such as platinum, rhodium, or
palladium, which is generally commercially available, can be used
as the hydrosilylation catalyst. Preferable examples of the
hydrosilylation catalyst include Karstedt catalyst, Spier catalyst,
and hexachloroplatinic acid; these compounds are well known in the
technical field.
The hydrosilylation catalyst to be added has only to be used in
such an amount that the transition metal in the catalyst accounts
for 10.sup.-9 to 1 mol % of the SiH groups; and preferable addition
amount is 10.sup.-7 to 10.sup.-3 mol %.
As shown in the following formula (IV), another method of producing
Compound (1-c) involves reacting Compound (1-a) with Compound
(1-0-4).
##STR00031##
A in the formula (1-0-3), (1-0-4), and (1-c) each represent a group
defined in the same manner as A in --OSi (A).sub.3 of R.sup.1 or
R.sup.2 of the formula (1) or (2).
In addition, a compound represented by the formula (2-a) can be
obtained by reacting Compound (1-0-1) with Compound (1-0-2) in such
a manner that a ratio of the number of moles (N) of Compound
(1-0-2) to the number of moles (M) of Compound (1-0-1) is 1 or
less, or preferably 0.1 to 1 as shown in the following formula (V).
Then, Compound (2-b) can be obtained from thus obtained Compound
(2-a) in the same manner as in the formula (II) or (III).
##STR00032##
The following procedure may be adopted: after Compound (1-0-1) and
Compound (1-0-2) have been reacted with each other at a ratio N/M
of more than 1 to provide Compound (1-a), Compound (1-a) is allowed
to react with Compound (1-0-1), or after Compound (1-0-1) and
Compound (1-0-2) have been allowed to react with each other at a
ratio M/N of more than 1 to provide Compound (2-a), Compound (2-a)
is allowed to react with Compound (1-0-2). Further, such reactions
may be alternately repeated.
It should be noted that a reaction similar to that described above
can be performed by reacting Compound (1-0-1') instead of Compound
(1-0-1) with Compound (1-0-2'). In a formula (1-0-1'), M represents
alkali metal, and preferably sodium or potassium.
##STR00033##
In this case, Compound (1-a') shown below or Compound (2-a) shown
above is obtained.
##STR00034##
In this case, X' in the formula (1-a') and (1-0-2') represent
halogen, and preferably chlorine. In addition, a reaction for
synthesizing Compound (1-c) from Compound (1-b) and for
synthesizing Compound (2-b) from Compound (2-a) can be performed in
the same manner as in the method of obtaining Compound (1-c) from
Compounds (1-b) and (1-0-3) represented by the above-mentioned
reaction formula (II) and the method of obtaining Compound (2-b)
from Compounds (2-a) and (1-0-3) represented by the above-mentioned
reaction formula (VI), respectively.
In addition, Compound (1-d) can also be obtained by performing such
reaction as shown below. Here, A represents a group defined in the
same manner as A in --OSi(A).sub.3 of the formula (1) and (2), and
X represents a group capable of reacting with silanol such as
halogen, alkoxy, or acetoxy. Specific examples of Compound (1-0-6)
include dichlorosilane and dichlorodiphenylsilane.
##STR00035##
The above-mentioned reaction between the compound represented by
the formula (1-0-1) and the compound represented by the formula
(1-0-2) can be performed in an organic solvent. The above-mentioned
reaction between the compound represented by the formula (1-0-1')
and the compound represented by the formula (1-0-2') can be
performed in an organic solvent.
An organic solvent to be used for production of the polysiloxane of
the present invention can be used as long as the organic solvent
does not inhibit the progress of the reaction for the production.
Specific examples of the organic solvent include: aromatic
hydrocarbons such as benzene, toluene, and xylene; aliphatic
hydrocarbons such as hexane and heptane; alcohols such as methanol,
ethanol, n-propanol, and iso-propanol; ethers such as dimethyl
ether, diethyl ether, tetrahydrofuran, and 1,4-dioxane; acetates
such as methyl acetate, ethyl acetate, and butyl acetate; amides
such as N,N-dimethylformamide, N,N-dimethylacetamide, and
N-methyl-2-pyrrolidone; ketones such as acetone, 2-butanone, and
methyl-iso-butyl ketone; acetonitrile; and dimethyl sulfoxide. Of
those, tetrahydrofuran and the acetates are preferable because each
of them can dissolve a raw material and a product. In addition, the
volume of the organic solvent, which is not particularly limited in
the present invention, is 0.01 to 100 parts by weight with respect
to 1 part by weight of Compound (1-0-1). The reaction may be
performed at room temperature, or may be performed under heating so
that the reaction is promoted. When heat generation due to the
reaction is not preferable, the reaction system may be cooled for
the purpose of controlling the reaction.
A polysiloxane in which silsesquioxanes and Q structures are
alternately bound [represented by each of the formula (1-a) and
(2-a)] can be produced by such reaction.
Next, a method of capping the resultant polysiloxane [represented
by each of the formula (1-a) and (2-a)] with a chlorosilane having
a group will be described. A polysiloxane having a reactive group
represented by each of the formula (1) and (2) can be produced by
applying a conventionally well-known method for reacting silanol
and the chlorosilane with each other.
A polymer obtained by the present invention, that is, the polymer
being obtained by introducing a skeleton having a cage-type
structure to the main chain of the polymer, is assumed to have
improved heat resistance and improved physical strength because
rigidity is imparted to the polymer by virtue of restriction on the
movement of the main chain. In addition, the polymer is expected to
have high optical permeability because of the specificity of its
structure. In addition, the polymer of the present invention can be
utilized in a wide variety of applications because the polymer is
expected to be excellent in, for example, solubility, heat
resistance, mechanical strength, optical permeability, gas
permeability, dielectric constant, flame retardancy, adhesiveness,
and processability. Examples of expected applications of the
polymer to electrical and electronic materials include: coating
agents for substrates, such as a metal elution-preventing film, a
gas barrier film, and an antireflection film; coating agents for
semiconductors, such as a liquid sealing agent and an interlayer
insulator; optical elements such as a microlens, a light-guiding
plate, and an optical waveguide material; display substrates; and
substrates for printed wiring. In addition, the polymer may be
blended with any other components such as an antioxidant, a
colorant, and a filler before use as required to such an extent
that the initial properties of the polymer are not impaired.
EXAMPLES
Hereinafter, the present invention will be described in more detail
by showing examples. However, the present invention is not limited
to these examples. It should be noted that "Ph" and "Me" in the
formula described in the examples represent "phenyl" and "methyl",
respectively. In addition, a nuclear magnetic resonance spectrum
was measured by using heavy tetrahydrofuran as a solvent and
tetramethylsilane as an internal standard substance at room
temperature unless otherwise stated.
Synthesis Example 1
<Synthesis of Compound (3-1)>
Phenyltrimethoxysilane (6.54 kg), sodium hydroxide (0.88 kg), water
(0.66 kg), and 2-propyl alcohol (26.3 liters) were loaded into a
reaction vessel equipped with a reflux condenser, a temperature
gauge, and a dropping funnel. In a stream of nitrogen, the heating
of the mixture was initiated while the mixture was stirred. After
the stirring had been continued for 6 hours from the initiation of
reflux, the mixture was left at rest at room temperature overnight.
Then, the reaction mixture was transferred to a filter, and was
filtered while being pressurized with nitrogen gas. The resultant
solid was washed with 2-propyl alcohol once and filtered, and then
the filtrate was dried under reduced pressure at 80.degree. C.,
whereby a white solid (3.3 kg) was obtained. The solid was defined
as Compound (3-1).
Synthesis Example 2
<Synthesis of Compound (3-2)>
Compound (3-1) obtained in Synthesis Example 1 (162 g) and ethyl
acetate (1,400 ml) was loaded into a reaction vessel equipped with
a dropping funnel, a temperature gauge, and a stirring machine, and
the mixture was stirred. In a stream of nitrogen, the reaction
mixture was cooled so as to have a temperature of 5.degree. C.
Then, acetic acid (42 g) was dropped to the reaction mixture while
the temperature of the reaction mixture was kept at 15.degree. C.
or lower, and the mixture was subjected to a reaction for 1 hour.
Next, acetic acid was neutralized with a saturated aqueous solution
of sodium hydrogen carbonate (100 g). After that, the reaction
mixture was washed with ion-exchanged water and treated with 1N
hydrochloric acid (10 g), and was then washed with ion-exchanged
water so as to be neutral. The resultant organic phase was
concentrated under reduced pressure at 50.degree. C., methyl
acetate (180 ml) was added to the residue, and the mixture was
stirred at room temperature for 2 hours. After that, the mixture
was filtered, thereby a white solid was obtained. The resultant
white solid was dried under reduced pressure at 50.degree. C.,
thereby Compound (3-2) as a powdery white solid (116 g) was
obtained.
.sup.1H NMR .delta.; 7.11-7.59 (m, 40H).
.sup.29Si NMR .delta.; -79.22, -69.11.
##STR00036##
Example 1
<Synthesis of Compound (1-2-1)>
56 g (52 mmol) of Compound (3-2) obtained in Synthesis Example 2,
42 g (159 mmol) of tetraacetoxysilane, and 900 ml of ethyl acetate
were loaded into a 2-L three-necked flask equipped with a reflux
condenser, a temperature gauge, and a stirring device. In a stream
of nitrogen, the mixture was heated to 60.degree. C. while being
stirred. After having been subjected to a reaction for 5 hours, the
mixture was cooled to room temperature. 100 g of water were charged
into the mixture, followed by stirring. After a solid had been
filtered, the residue was concentrated at 50.degree. C., thereby
about 850 ml of the residue were removed by distillation. Then, the
resultant reaction mixture was filtered, thereby a solid was
obtained. The resultant solid was dried under reduced pressure at
70.degree. C. for 2 hours, thereby 49 g of Compound (1-2-1) as a
white solid were obtained.
.sup.1H NMR .delta. (ppm); 6.15 (s, 4H), 7.09-7.70 (m, 40H).
.sup.29Si NMR .delta. (ppm); -89.8, -79.28, -78.75.
##STR00037##
Example 2
<Synthesis of Compound (1-4-1)>
23 g (240 mmol) of chlorodimethylsilane and toluene (400 ml) were
loaded into a 1-L four-necked flask equipped with a reflux
condenser, a temperature gauge, a dropping funnel, and a stirring
device. In a stream of nitrogen, 22 g (216 mmol) of triethylamine
were dropped to the mixture while the mixture was stirred. Next, 48
g (40 mmol) of Compound (1-2-1) were dissolved in ethyl acetate
(210 ml), and the solution was dropped to the reaction mixture so
that the temperature of the reaction mixture should be kept at
35.degree. C. or lower. After the mixture had been continuously
subjected to a reaction for 3 hours, water (50 g) was added to the
mixture, and followed by continuous stirring for 30 minutes. Then,
the mixture was separated into an organic phase and an aqueous
phase with a separating funnel. The resultant organic phase was
washed with water so as to be neutral, and was then dried with
anhydrous magnesium sulfate. Next, anhydrous magnesium sulfate was
removed by filtration, and then the residue was concentrated under
reduced pressure at 50.degree. C. Methyl alcohol (120 ml) was added
to the resultant residue, and the mixture was stirred for 4 hours.
After that, the mixture was filtered, thereby a solid was obtained.
The resultant white solid was dried under reduced pressure at
70.degree. C. for 2 hours, thereby Compound (1-4-1) as a white
solid was obtained.
.sup.1H NMR .delta. (ppm); 0.11 (s, 24H), 4.70-4.73 (m, 4H),
7.15-7.58 (m, 40H).
.sup.29Si NMR .delta. (ppm); -106.22, -79.38, -78.95, -3.04.
##STR00038##
Example 3
<Synthesis of Compound (1-5-1)>
47 g (33 mmol) of Compound (1-4-1) synthesized in Example 2, 23 g
(202 mmol) of allylglycidylether, and toluene (70 g) were loaded
into a 200-ml four-necked flask equipped with a reflux condenser, a
temperature gauge, a dropping funnel, a septum cap made of silicon,
and a stirrer. In a stream of nitrogen, the mixture was heated to
40.degree. C. while being stirred. A Karstedt's catalyst (20 .mu.l)
was added to the mixture with a microsyringe to initiate the
reaction. After the completion of heat generation had been
confirmed, the mixture was heated to be brought into a reflux
state. The mixture was subjected to a reaction for 3 hours, and
then part of the reaction mixture was sampled and subjected to
infrared absorption spectral analysis. The disappearance of a peak
at 2138 cm.sup.-1 originating from Si--H group was confirmed, and
the time point of the disappearance was defined as the end point of
the reaction. Then, the reaction mixture was concentrated under
reduced pressure at 120.degree. C. for 1 hour and at 130.degree. C.
for 1 hour, thereby 62 g of a viscous liquid were obtained. The
resultant viscous liquid was dissolved in methyl acetate (250 ml),
and then powdery active carbon (1.3 g) was added to the solution.
After having been stirred at 40.degree. C. for 1 hour, the mixture
was filtered, thereby active carbon was removed. The resultant
reaction mixture was concentrated under reduced pressure at
80.degree. C., thereby a colorless, transparent, viscous liquid (61
g) was obtained. Next, the resultant viscous liquid was dissolved
in ethyl acetate (40 ml), and the solution was reprecipitated from
n-heptane (1,200 ml). The produced solid was filtered, and then the
residue was dried under reduced pressure at 40.degree. C. for 3
hours, thereby Compound (1-5-1) as a white solid (55 g) was
obtained.
.sup.1H NMR (CDCl.sub.3): .delta. (ppm); 0.04 (s, 24H), 0.48-0.52
(m, 8H), 1.46-1.53 (m, 8 H), 2.46 (dd, 4H), 2.67 (t, 4H), 2.96-3.00
(m, 4H), 3.09-3.17 (m, 12H), 3.45 (dd, 4H), 7.18 (t, 8H), 7.25 (t,
8H), 7.33 (t, 4H), 7.39 (t, 4H), 7.43 (d, 8 H), 7.57 (d, 8H).
.sup.29Si NMR (CDCl.sub.3): .delta. (ppm); -106.95, -79.38, -79.12,
11.45
##STR00039##
Example 4
<Synthesis of Compound (1-6-1)>
1.0 g (0.7 mmol) of Compound (1-4-1) produced in Example 2, 0.4 g
(3.2 mmol) of 4-vinyl-1-cyclohexene-1,2-epoxide, and toluene (1.0
g) were loaded into a 50-ml four-necked flask equipped with a
reflux condenser, a temperature gauge, a dropping funnel, a septum
cap made of silicon, and a stirrer. In a stream of nitrogen, the
mixture was heated to 60.degree. C. while being stirred. A
Karstedt's catalyst (0.9 .mu.l) was added to the mixture with a
microsyringe to initiate the reaction. After the completion of heat
generation had been confirmed, the mixture was heated to be brought
into a reflux state. The mixture was subjected to a reaction for 2
hours, and then part of the reaction mixture was sampled and
subjected to infrared absorption spectral analysis. The
disappearance of a peak at 2137 cm.sup.-1 originating from Si--H
group was confirmed, and the time point of the disappearance was
defined as the end point of the reaction. Then, the reaction
mixture was concentrated under reduced pressure at 80.degree. C.
for 2 hours, thereby a yellow solid (1.4 g) was obtained. The
resultant yellow solid was dissolved in ethyl acetate (1.4 g).
After that, the solution was dropped to normal hexane (28 g),
followed by stirring. Then, the mixture was filtered with a
membrane filter having pore size of 0.1 .mu.m, and the filtrate was
concentrated under reduced pressure at 80.degree. C. for 2 hours,
thereby Compound (1-6-1) as a white solid (1.3 g) was obtained.
.sup.1H-NMR (CDCl.sub.3): .delta. (ppm); 0.01 (s, 24H), 0.40-0.44
(m, 8H), 0.52-0.63 (m, 2 H), 0.82-0.87 (m, 4H), 0.95-1.26 (m, 18H),
1.43-1.49 (m, 2H), 1.59-1.78 (m, 6H), 1.94 (dd, 4H), 2.91-3.01 (m,
8H), 7.17 (t, 8H), 7.25 (t, 8H), 7.33 (t, 4H), 7.38-7.43 (m, 12H),
7.56 (d, 8H).
.sup.29Si-NMR (CDCl.sub.3): .delta. (ppm); -106.92, -79.41, -79.18,
11.26, 11.28, 11.34, 11.36.
##STR00040##
Example 5
<Synthesis of Compound (1-3-2)>
6.4 g (6.0 mmol) of Compound (3-2) obtained in Synthesis Example 2,
2.2 g (8.3 mmol) of tetraacetoxysilane, and ethyl acetate (120 ml)
were loaded into a reaction vessel equipped with a reflux
condenser, a temperature gauge, and a stirring device. In a stream
of nitrogen, the mixture was heated to 75.degree. C. while being
stirred, and was then subjected to the reaction for 4 hours. After
the mixture had been cooled to room temperature, 1.1 g (4.2 mmol)
of tetraacetoxysilane were added to the mixture, followed by
heating to 75.degree. C. to perform the reaction for 1 hour. Then,
the resultant was cooled to room temperature. After that, water was
added to the resultant, and the mixture was centrifuged to be
separated into a solid and a liquid. Toluene (40 ml) was added to
the resultant solution, and the mixture was centrifuged again to be
separated into a solid and a liquid; the operation was repeated 3
times. A filtrate thus obtained was concentrated under reduced
pressure, thereby Compound (1-3-2) as a white solid was
obtained.
.sup.1H-NMR .delta. (ppm); 6.17 (s, 4H).6.83-7.69 (m, 80H).
.sup.29Si-NMR .delta. (ppm); -108.91, -89.70, -89.66, -78.84,
-78.51, -77.67.
##STR00041##
Example 6
<Synthesis of Compound (2-1-1)>
1 g (0.9 mmol) of Compound (3-2) obtained in Synthesis Example 2,
0.8 g (3.0 mmol) of tetraacetoxysilane, and ethyl acetate (40 ml)
were loaded into a reaction vessel equipped with a reflux
condenser, a temperature gauge, and a stirring device. In a stream
of nitrogen, the mixture was heated to 55.degree. C. while being
stirred, and was then subjected to a reaction for 5 hours. Then,
the mixture was cooled to room temperature. After that, 6.4 g (6.0
mmol) of Compound (3-2) were dissolved in tetrahydrofuran (20 ml),
and the obtained solution was added to the mixture, followed by
heating to 55.degree. C. to perform the reaction for 6 hours. Then,
the resultant was cooled to room temperature. After that, it was
neutralized, washed with water, filtered, and concentrated, thereby
a white solid (7.8 g) was obtained. Next, ethyl acetate (30 ml) was
added to the resultant white solid, followed by stirring. After
that, the mixture was separated into a solid and a liquid. Then,
toluene (40 ml) was added to the resultant filtrate, and the
produced solid was separated by filtration. Then, hexane was added
to the filtrate for recrystallization, thereby Compound (2-1-1) as
a white solid was obtained.
.sup.29Si-NMR .delta. (ppm); -109.10, -78.99, -78.58, -77.81,
-77.68, -69.02.
* * * * *